CN113024928B - Photochromic laser color change material, preparation method and application thereof - Google Patents
Photochromic laser color change material, preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of secondary processing of polymer materials, and particularly relates to a photochromic laser color change material, and a preparation method and application thereof. The photochromic laser color-changing material provided by the invention is prepared from the following raw materials in parts by weight: 60-99 parts of matrix polymer, 0.05-10 parts of carbon material and 1-30 parts of core-shell structure microspheres; the shell material of the core-shell structure microsphere is thermosetting resin, and the core of the core-shell structure microsphere is composed of a photochromic compound, a solvent and a light stabilizer. Experiments prove that after the photochromic laser color-changing material is thermally processed into polymer parts with different forms, the photochromic laser color-changing material can be marked on the surface of a dark-colored part by laser to obtain light-colored marks, and the marks can be changed into colors under visible light and/or ultraviolet light. The preparation method of the photochromic laser color-changing material disclosed by the invention is simple and easy to operate, widens the application field of the laser marking polymer, is very suitable for large-scale industrial production, and has good economic benefit.
Description
Technical Field
The invention belongs to the field of secondary processing of polymer materials, and particularly relates to a preparation method and application of a photochromic laser color change material.
Background
The anti-counterfeiting mark is a mark which can be pasted, printed by a national 315 product anti-counterfeiting inquiry center, pasted on the surface of an article or an accessory of a package (such as a commodity hang tag, a qualification certificate and an anti-counterfeiting certificate card) and has an anti-counterfeiting function. Most of the existing anti-counterfeiting marks are formed by adding various variable color masks on the surface of a product.
At present, the anti-counterfeiting measures include traditional printing technologies such as water drop color change (or disappearance), high-temperature color change (or disappearance), ray burying, ultraviolet irradiation color change (or disappearance) and the like, and digital anti-counterfeiting technologies such as two-dimensional codes, inquiry codes and the like. The technique of ultraviolet radiation color change (or disappearance) generally utilizes molecules having fluorescent properties that are one color in visible light and another color in ultraviolet light due to fluorescence emission.
However, the common anti-counterfeiting mark as a printed matter has mature preparation technology and too simple manufacturing technology, which leads to easy imitation and loss of anti-counterfeiting function. Therefore, there is a need to develop new anti-counterfeit mark manufacturing technology.
Laser marking is a method of irradiating a material with high-energy laser light to cause carbonization, discoloration, vaporization, foaming, etc. of the surface of the material, thereby leaving a permanent mark. Compared with traditional methods such as ink printing, screen printing, stamping, hot stamping and the like, laser marking has the advantages of high precision, no contact, high efficiency, low cost, cleanness, no pollution and the like, and is gradually becoming a more popular mode. Since the appearance of a material such as a polymer after laser irradiation is related to various process conditions such as the composition and laser irradiation parameters thereof, it is difficult to copy the material. If the method for processing the polymer by laser is applied to the anti-counterfeiting mark, the difficulty of imitating the anti-counterfeiting mark can be greatly increased.
At present, the laser marking method can generate white or light-colored marks on the surface of a dark-colored (black, black gray or gray) polymer material, and the principle is that after a laser absorber absorbs laser energy, a dark-colored polymer matrix is subjected to complex chemical and physical changes under the action of laser to generate the white or light-colored marks. However, such laser-processed white or light-colored marks cannot be directly used as anti-counterfeit marks themselves, and there is a need for increasing the function of changing color under specific conditions by modifying the molecular structure or the composition thereof.
The new application scenes such as the personalized anti-counterfeiting mark and the like put forward the following performance requirements on the manufacturing materials of the anti-counterfeiting mark: the need of being able to produce white or light-colored marks on the surface of polymer materials with dark colors by using laser and to make the marks change colors (such as red, blue, yellow, green, purple, etc.) under certain stimulation.
The Chinese patent of invention "laser marking of a CN200780041444.8 pigmented substrate" provides a composition of a polymer and a colorant, wherein the polymer can form a mark under laser irradiation, and the colorant in the mark can change color under visible light or ultraviolet light. However, the composition of the polymer material with the dark color is different from that of the polymer material disclosed in the invention, and the process of forming the mark by the polymer material with the dark color under laser irradiation can absorb a large amount of heat, thereby destroying the colorant. The addition of the colorants disclosed in this patent to dark colored polymeric materials is therefore not capable of meeting the above performance requirements.
Accordingly, there is a need in the art for a novel photochromic laser color-changing material that can conveniently produce a white or light-colored mark on a dark polymer using a laser and can change into a colored mark under certain external condition stimuli (e.g., ultraviolet light, visible light, etc.). However, such materials do not exist in the prior art.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a photochromic laser color change material, a preparation method and application thereof. The method aims to combine core-shell structure microspheres, carbon materials and matrix polymers to obtain a material which can be marked by laser and the obtained mark can change color under visible light and/or ultraviolet light.
A photochromic laser color-changing material is prepared from the following raw materials in parts by weight:
60 to 99 parts of matrix polymer,
0.05 to 10 parts of carbon material,
1-30 parts of core-shell structure microspheres;
the shell material of the core-shell structure microsphere is thermosetting resin, and the core of the core-shell structure microsphere is composed of a photochromic compound, a solvent and a light stabilizer.
Preferably, the feed additive is prepared from the following raw materials in parts by weight:
93.8 to 96.95 portions of matrix polymer,
0.05 to 0.2 portion of carbon material,
3-6 parts of core-shell structure microspheres.
Preferably, the feed additive is prepared from the following raw materials in parts by weight:
93.8 to 96.8 portions of matrix polymer,
0.2 part of carbon material (C),
3-6 parts of core-shell structure microspheres.
Preferably, the matrix polymer is selected from the group consisting of polyethylene, polypropylene, ethylene-propylene copolymer, polyoxymethylene, polystyrene, styrene-acrylonitrile copolymer, styrene-methyl methacrylate copolymer, polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate, polycarbonate, polyester elastomer, polybutylene succinate-butylene terephthalate, polybutylene succinate-butylene adipate, polymethacrylate-butadiene-styrene copolymer, styrene-acrylonitrile-acrylate copolymer, poly (ethylene-co-butylene-co-acrylate), poly (ethylene-co-methacrylate), poly (ethylene-co-acrylonitrile-co-methacrylate), poly (ethylene-co-acrylonitrile-methacrylate), poly (ethylene-co-methacrylate), poly (ethylene-butylene-methacrylate), poly (ethylene-co-terephthalate), poly (ethylene-co-butylene-adipate), poly (butylene-succinate), poly (butylene-methacrylate), poly (butylene-terephthalate), poly (butylene terephthalate), poly (styrene), poly (butylene (styrene), poly (butylene terephthalate), poly (butylene (styrene), poly (butylene), poly (styrene), poly (butylene), at least one of methacrylate-butadiene-styrene, ABS, nylon, polyolefin elastomer, ethylene-vinyl alcohol copolymer, ethylene-vinyl acetate copolymer, SEBS, SEPS, SEEPS;
preferably, the carbon material is at least one selected from graphite, graphene, carbon black, and carbon nanotubes.
Preferably, the thermosetting resin is selected from at least one of urea-formaldehyde resin, phenol-formaldehyde resin, melamine-formaldehyde resin, chitosan, epoxy resin or unsaturated or polyester resin;
and/or the photochromic compound is at least one selected from a spiropyran compound, a spirooxazine compound, a fulgide compound, a diarylethene compound, an azobenzene compound, a Schiff base compound, a dianthracene ketone compound, a fluorescent hydrocarbon compound, a triphenylmethane compound or a cholesteric liquid crystal compound;
and/or the solvent is selected from at least one of liquid paraffin, ethyl heptanoate, ethyl octanoate, ethyl nonanoate, ethyl decanoate, ethyl palmitate, methyl heptanoate, methyl octanoate, methyl nonanoate, methyl decanoate, methyl palmitate, dichloromethane, trichloromethane, cyclohexane, benzene, toluene, xylene or decalin;
and/or, the light stabilizer is selected from at least one of light stabilizer 770, light stabilizer 944, light stabilizer 292, light stabilizer 622, light stabilizer 144, light stabilizer 123 or bisphenol A.
Preferably, the particle size of the core-shell structure microsphere is 500 nm-100 μm; preferably 800 nm-80 μm;
the invention also provides a preparation method of the photochromic laser color-changing material, which comprises the following steps: and uniformly mixing the matrix polymer, the carbon material and the core-shell structure microspheres, and then melting, extruding and granulating to obtain the core-shell structure microsphere.
Preferably, the melting and extrusion is carried out in an internal mixer or extruder, and/or the extrusion conditions are at a temperature of 160 ℃ to 270 ℃.
The invention also provides the application of the photochromic laser color change material in manufacturing the personalized anti-counterfeiting mark.
The invention also provides a preparation method of the anti-counterfeiting mark, which is prepared by irradiating the photochromic laser color-changing material with laser and generating patterns or characters with lighter color than the original surface.
Preferably, the photochromic laser color-changing material is used for generating the following changes: under the irradiation of laser, the photochromic laser color-changing material generates patterns or characters with lighter color than the original surface, and the patterns or characters can change the color under the ultraviolet light and/or visible light.
Preferably, the laser is passed through CO2A laser (emission wavelength 10.6 μm), Nd: YAG laser, Nd: YVO4 laser (emission wavelengths 1064, 532, 355 and 266nm), excimer laser (F2(157nm), ArF (193nm), KrCl (222nm), KrF (248nm), XeCl (308nm) and XeF (351nm)), fiber laser, diode array laser or diode laser emission; the wavelength of the laser is 157nm-10.6 mu m;
preferably, the laser is emitted by a pulsed Nd: YAG laser or a pulsed fiber laser; the wavelength of the laser is 1064nm, 532nm or 355 nm.
The invention also provides the anti-counterfeiting mark obtained by the preparation method.
In the present invention, "light color" means various white, pale white, silvery white, pale gray, silver, various silvery gray, and the like. "colored" refers to a single common color such as red, blue, yellow, green, or purple, or various mixtures thereof. It should be noted that colors such as black, grayblack, gray, white, pale gray, etc. do not fall within the scope of the color defined in the present invention.
According to the technical scheme, white or light-colored patterns or characters can be marked on the dark-colored polymer by using laser, the photochromic compound is wrapped inside the core-shell structure microsphere, and the photochromic compound cannot be damaged in the process that the dark-colored polymer is irradiated by the laser and generates heat. The formed white or light patterns or characters can be changed into colorful patterns or characters under the stimulation of ultraviolet light and/or visible light. Therefore, the material of the invention is particularly suitable for preparing anti-counterfeiting marks. The photochromic laser color change material has the advantages of simple and efficient preparation process, simple and convenient operation, safety, environmental protection and low energy consumption, and is very suitable for industrial large-scale production.
Obviously, many modifications, substitutions, and variations are possible in light of the above teachings of the invention, without departing from the basic technical spirit of the invention, as defined by the following claims.
The present invention will be described in further detail with reference to the following examples. This should not be understood as limiting the scope of the above-described subject matter of the present invention to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.
Drawings
FIG. 1 is a photograph showing the effect of laser marking on a sample plate made of the photochromic laser-color-change material of example 7.
FIG. 2 is a photograph showing the color change effect of a sample plate made of the photochromic laser-color change material in example 7 under partial UV irradiation.
Detailed Description
The starting materials used in the practice of the present invention are all known products and are obtained by purchasing commercially available products.
(1) The device information is as follows:
a double-screw extruder, wherein the diameter of a screw is 35mm, the length-diameter ratio of the screw is 36:1, and the extruder is produced by Nanjing Jennent electromechanical limited company;
injection molding machine, model K-TEC 40, produced by Miracolon International Inc.;
laser marking machine, model MK-GQ10B, fiber pulse laser marking machine, laser maximum power 10W, laser wavelength 1064 nm.
(2) The specific information for the matrix polymer used to prepare the master plate is as follows:
polyethylene (PE): the metallocene petrochemical, TR144, a high density polyethylene;
polypropylene (PP): china petrochemical lanzhou division, T30S;
polyoxymethylene (POM): shenhua MC90, a copolyformaldehyde;
polymethyl methacrylate: degussa 8NDF 21.
(3) The product information of the core-shell structure microspheres is as follows:
the core-shell structure microspheres are purchased from Dazhangjiyuan new materials science and technology Co. The product models are respectively PCC-1, PCC-1-2, PCC-1-3, PCC-2, PCC-3, PCC-4, PCC-5, PCC-6 and PCC-7.
Example 1
Matrix polymer: polyethylene (PE), ruthinized TR144, a High Density Polyethylene (HDPE);
carbon material: graphene;
core-shell structure microspheres (PCC-1-2): when stimulated by ultraviolet rays, the color of the material is changed from colorless to blue. The melamine formaldehyde resin is the shell of the microsphere, the photochromic compound is a spiropyran compound, the solvent is ethyl decanoate, the light stabilizer is bisphenol A, and the three form the core of the microsphere. The particle size of the core-shell microsphere is 900 nm.
100 parts by weight of HDPE, 3 parts by weight of core-shell structure microspheres and 0.05 part by weight of graphene are placed in a high-speed mixer and uniformly mixed; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the photochromic laser color change material. The temperature in the blending extrusion processing process is controlled between 160 ℃ and 220 ℃;
and then, directly carrying out injection molding on the obtained photochromic laser color change material granules in an injection molding machine, controlling the injection molding temperature to be 180-230 ℃, and preparing a black and gray standard sample plate.
Example 2
Matrix polymer: polyethylene (PE), ruthinized TR144, a High Density Polyethylene (HDPE);
carbon material: carbon black, N330;
core-shell structure microspheres (PCC-3): when stimulated by ultraviolet rays, the color of the material is changed from colorless to blue. The chitosan is the shell of the microsphere, the photochromic compound is a spiropyran compound, the solvent is ethyl decanoate, the light stabilizer is bisphenol A, and the three form the core of the microsphere. The grain diameter of the core-shell microsphere is 10 μm.
100 parts by weight of HDPE, 3 parts by weight of core-shell structure microspheres and 0.05 part by weight of carbon black are placed in a high-speed mixer and uniformly mixed; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the photochromic laser color change material. The temperature in the blending extrusion processing process is controlled between 160 ℃ and 220 ℃;
and then, directly carrying out injection molding on the obtained photochromic laser color change material granules in an injection molding machine, controlling the injection molding temperature to be 180-230 ℃ and preparing a black standard sample plate.
Example 3
Matrix polymer: polyoxymethylene (POM), shenhua MC90, a copolyformaldehyde;
carbon material: graphene;
core-shell structure microspheres (PCC-4): when stimulated by ultraviolet rays, the color of the material is changed from colorless to red. The epoxy resin is the shell of the microsphere, the photochromic compound is a diarylethene compound, the solvent is toluene, and the light stabilizer is light stabilizer 622, and the three form the core of the microsphere. The particle size of the core-shell microspheres is 95 μm.
Putting 100 parts by weight of polyformaldehyde resin, 3 parts by weight of core-shell structure microspheres and 0.1 part by weight of graphene into a high-speed mixer, and uniformly mixing; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the photochromic laser color change material. The temperature in the blending extrusion processing process is controlled between 170 ℃ and 240 ℃;
and then, directly carrying out injection molding on the obtained photochromic laser color change material granules in an injection molding machine, controlling the injection molding temperature to be 180-250 ℃ and preparing a black standard sample plate.
Example 4
Matrix polymer: polyoxymethylene (POM), shenhua MC90, a copolyformaldehyde;
carbon material: carbon black, N330;
core-shell structure microspheres (PCC-5): when stimulated by ultraviolet rays, the color of the material is changed from colorless to red. The urea-formaldehyde resin is the shell of the microsphere, the photochromic compound is a diarylethene compound, the solvent is toluene, and the light stabilizer is the light stabilizer 622, and the three form the core of the microsphere. The particle size of the core-shell microspheres is 50 μm.
Putting 100 parts by weight of polyformaldehyde resin, 3 parts by weight of core-shell structure microspheres and 0.1 part by weight of carbon black into a high-speed mixer, and uniformly mixing; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the photochromic laser color change material. The temperature in the blending extrusion processing process is controlled between 170 ℃ and 240 ℃;
and then, directly carrying out injection molding on the obtained photochromic laser color change material granules in an injection molding machine, controlling the injection molding temperature to be 180-250 ℃ and preparing a black standard sample plate.
Example 5
Matrix polymer: polymethyl methacrylate, degussa 8NDF 21;
carbon material: graphite with a mesh number of 2000;
core-shell structure microspheres (PCC-1): when stimulated by ultraviolet rays, the color of the material is changed from colorless to red. The melamine formaldehyde resin is the shell of the microsphere, the photochromic compound is a diarylethene compound, the solvent is toluene, and the light stabilizer is light stabilizer 622, and the three form the core of the microsphere. The particle size of the core-shell microsphere is 20 μm.
Putting 100 parts by weight of polymethyl methacrylate, 3 parts by weight of core-shell structure microspheres and 0.2 part by weight of graphite into a high-speed mixer, and uniformly mixing; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the photochromic laser color change material. The temperature in the blending extrusion processing process is controlled between 200 ℃ and 250 ℃;
and then, directly carrying out injection molding on the obtained photochromic laser color change material granules in an injection molding machine, controlling the injection molding temperature to be 210-260 ℃ and preparing a black standard sample plate.
Example 6
Matrix polymer: polymethyl methacrylate, degussa 8NDF 21;
carbon material: carbon black, N330;
core-shell structure microspheres (PCC-1): when stimulated by ultraviolet rays, the color of the material is changed from colorless to red. The melamine formaldehyde resin is the shell of the microsphere, the photochromic compound is a diarylethene compound, the solvent is toluene, and the light stabilizer is light stabilizer 622, and the three form the core of the microsphere. The particle size of the core-shell microsphere is 20 μm.
Putting 100 parts by weight of polymethyl methacrylate, 3 parts by weight of core-shell structure microspheres and 0.2 part by weight of carbon black into a high-speed mixer, and uniformly mixing; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the photochromic laser color change material. The temperature in the blending extrusion processing process is controlled between 200 ℃ and 250 ℃;
and then, directly carrying out injection molding on the obtained photochromic laser color change material granules in an injection molding machine, controlling the injection molding temperature to be 210-260 ℃ and preparing a black standard sample plate.
Example 7
Matrix polymer: polypropylene (PP), china petrochemical, lanzhou division, T30S;
carbon material: graphene;
core-shell structure microspheres (PCC-1): when being stimulated by ultraviolet rays, the color of the material is changed from colorless to red. The melamine formaldehyde resin is the shell of the microsphere, the photochromic compound is a diarylethene compound, the solvent is toluene, and the light stabilizer is light stabilizer 622, and the three form the core of the microsphere. The particle size of the core-shell microsphere is 20 μm.
Placing 100 parts by weight of polypropylene resin, 6 parts by weight of core-shell structure microspheres and 0.2 part by weight of graphene into a high-speed mixer, and uniformly mixing; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the photochromic laser color change material. The temperature in the blending extrusion processing process is controlled between 170 ℃ and 240 ℃;
and then, directly carrying out injection molding on the obtained photochromic laser color change material granules in an injection molding machine, controlling the injection molding temperature to be 180-250 ℃ and preparing a black standard sample plate.
Example 8
Matrix polymer: polypropylene (PP), china petrochemical, lanzhou division, T30S;
carbon material: the multi-walled carbon nanotube has a tube diameter of 3-15 nm and a length of 15-30 μm;
core-shell structure microspheres (PCC-1): when stimulated by ultraviolet rays, the color of the material is changed from colorless to red. The melamine formaldehyde resin is the shell of the microsphere, the photochromic compound is a diarylethene compound, the solvent is toluene, and the light stabilizer is light stabilizer 622, and the three form the core of the microsphere. The particle size of the core-shell microsphere is 20 μm.
Placing 100 parts by weight of polypropylene resin, 6 parts by weight of core-shell structure microspheres and 0.2 part by weight of carbon nanotubes in a high-speed mixer for uniform mixing; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the photochromic laser color change material. The temperature in the blending extrusion processing process is controlled between 170 ℃ and 240 ℃;
and then, directly carrying out injection molding on the obtained photochromic laser color change material granules in an injection molding machine, controlling the injection molding temperature to be 180-250 ℃ and preparing a black standard sample plate.
Comparative example 1
Matrix polymer: polyethylene (PE), ruthinized TR144, a High Density Polyethylene (HDPE);
carbon material: graphene;
putting 100 parts by weight of HDPE and 0.05 part by weight of graphene into a high-speed mixer, and uniformly mixing; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the blend. The temperature in the blending extrusion processing process is controlled between 160 ℃ and 220 ℃;
and then, directly carrying out injection molding on the obtained granules in an injection molding machine, controlling the injection molding temperature to be 180-230 ℃, and preparing a black and gray standard sample plate.
Comparative example 2
Matrix polymer: polyethylene (PE), ruthinized TR144, a High Density Polyethylene (HDPE);
carbon material: carbon black, N330;
putting 100 parts by weight of HDPE and 0.05 part by weight of carbon black into a high-speed mixer, and uniformly mixing; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the blend. The temperature in the blending extrusion processing process is controlled between 160 ℃ and 220 ℃;
and then, directly carrying out injection molding on the obtained granules in an injection molding machine, controlling the injection molding temperature to be 180-230 ℃, and preparing a black standard sample plate.
Comparative example 3
Matrix polymer: polyoxymethylene (POM), shenhua MC90, a copolyformaldehyde;
core-shell structure microspheres (PCC-1): when stimulated by ultraviolet rays, the color of the material is changed from colorless to red. The melamine formaldehyde resin is the shell of the microsphere, the photochromic compound is a diarylethene compound, the solvent is toluene, and the light stabilizer is light stabilizer 622, and the three form the core of the microsphere. The particle size of the core-shell microsphere is 20 μm.
Putting 100 parts by weight of polyformaldehyde resin and 3 parts by weight of core-shell structure microspheres into a high-speed mixer, and uniformly mixing; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the blend. The temperature in the blending extrusion processing process is controlled between 170 ℃ and 240 ℃;
and then, directly carrying out injection molding on the obtained granules in an injection molding machine, controlling the injection molding temperature to be 180-250 ℃ and preparing an off-white standard sample plate.
Comparative example 4
Matrix polymer: polyoxymethylene (POM), shenhua MC90, a copolyformaldehyde;
core-shell structure microspheres (PCC-1-2): when stimulated by ultraviolet rays, the color of the material is changed from colorless to blue. The melamine formaldehyde resin is the shell of the microsphere, the photochromic compound is a spiropyran compound, the solvent is ethyl decanoate, the light stabilizer is bisphenol A, and the three form the core of the microsphere. The particle size of the core-shell microsphere is 900 nm.
Placing 100 parts by weight of polypropylene resin and 3 parts by weight of core-shell structure microspheres in a high-speed mixer for uniformly mixing; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the blend. The temperature in the blending extrusion processing process is controlled between 170 ℃ and 240 ℃;
and then, directly carrying out injection molding on the obtained granules in an injection molding machine, controlling the injection molding temperature to be 180-250 ℃ and preparing an off-white standard sample plate.
Comparative example 5
Matrix polymer: polymethyl methacrylate, degussa 8NDF 21;
carbon material: graphene;
core-shell structure microspheres (PCC-1): when stimulated by ultraviolet rays, the color of the material is changed from colorless to red. The melamine formaldehyde resin is the shell of the microsphere, the photochromic compound is a diarylethene compound, the solvent is toluene, and the light stabilizer is light stabilizer 622, and the three form the core of the microsphere. The particle size of the core-shell microsphere is 20 μm.
Putting 100 parts by weight of polymethyl methacrylate, 0.3 part by weight of core-shell structure microspheres and 5 parts by weight of graphene into a high-speed mixer, and uniformly mixing; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the photochromic laser color change material. The temperature in the blending extrusion processing process is controlled between 200 ℃ and 250 ℃;
and then, directly carrying out injection molding on the obtained photochromic laser color change material granules in an injection molding machine, controlling the injection molding temperature to be 210-260 ℃ and preparing a black standard sample plate.
Comparative example 6
Matrix polymer: polymethyl methacrylate, degussa 8NDF 21;
carbon material: carbon black, N330;
core-shell structure microspheres (PCC-1): when stimulated by ultraviolet rays, the color of the material is changed from colorless to red. The melamine formaldehyde resin is the shell of the microsphere, the photochromic compound is a diarylethene compound, the solvent is toluene, and the light stabilizer is light stabilizer 622, and the three form the core of the microsphere. The particle size of the core-shell microsphere is 20 μm.
Putting 100 parts by weight of polymethyl methacrylate, 0.3 part by weight of core-shell structure microspheres and 5 parts by weight of carbon black into a high-speed mixer, and uniformly mixing; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the photochromic laser color change material. The temperature in the blending extrusion processing process is controlled between 200 ℃ and 250 ℃;
and then, directly carrying out injection molding on the obtained photochromic laser color change material granules in an injection molding machine, controlling the injection molding temperature to be 210-260 ℃ and preparing a black standard sample plate.
Comparative example 7
Matrix polymer: polypropylene (PP), china petrochemical, lanzhou division, T30S;
carbon material: the multi-walled carbon nanotube has a tube diameter of 3-15 nm and a length of 15-30 μm;
core-shell structure microspheres (PCC-1-2): when stimulated by ultraviolet rays, the color of the material is changed from colorless to blue. The melamine formaldehyde resin is the shell of the microsphere, the photochromic compound is a spiropyran compound, the solvent is ethyl decanoate, the light stabilizer is bisphenol A, and the three form the core of the microsphere. The particle size of the core-shell microsphere is 900 nm.
Placing 100 parts by weight of polypropylene resin, 6 parts by weight of core-shell structure microspheres and 0.02 part by weight of carbon nanotubes in a high-speed mixer, and uniformly mixing; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the photochromic laser color change material. The temperature in the blending extrusion processing process is controlled between 170 ℃ and 240 ℃;
and then, directly carrying out injection molding on the obtained photochromic laser color change material granules in an injection molding machine, controlling the injection molding temperature to be 180-250 ℃ and preparing a black and gray standard sample plate.
Comparative example 8
Matrix polymer: polypropylene (PP), china petrochemical, lanzhou division, T30S;
carbon material: graphite with a mesh number of 2000;
core-shell structure microspheres (PCC-1): when being stimulated by ultraviolet rays, the color of the material is changed from colorless to red. The melamine formaldehyde resin is the shell of the microsphere, the photochromic compound is a diarylethene compound, the solvent is toluene, and the light stabilizer is light stabilizer 622, and the three form the core of the microsphere. The particle size of the core-shell microsphere is 20 μm.
100 parts by weight of polypropylene resin, 6 parts by weight of core-shell structure microspheres and 15 parts by weight of graphite powder are placed in a high-speed mixer and uniformly mixed; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the photochromic laser color change material. The temperature in the blending extrusion processing process is controlled between 170 ℃ and 240 ℃;
and then, directly carrying out injection molding on the obtained photochromic laser color change material granules in an injection molding machine, controlling the injection molding temperature to be 180-250 ℃ and preparing a black standard sample plate.
Comparative example 9
Matrix polymer: polypropylene (PP), china petrochemical, lanzhou division, T30S;
carbon material: the multi-walled carbon nanotube has a tube diameter of 3-15 nm and a length of 15-30 μm;
core-shell structure microspheres (PCC-6): when stimulated by ultraviolet rays, the color of the material is changed from colorless to blue. The polystyrene resin is the shell of the microsphere, the photochromic compound is a spiropyran compound, the solvent is ethyl decanoate, and the light stabilizer is bisphenol A, and the three form the core of the microsphere. The grain diameter of the core-shell microsphere is 600 nm.
Placing 100 parts by weight of polypropylene resin, 6 parts by weight of core-shell structure microspheres and 0.02 part by weight of carbon nanotubes in a high-speed mixer, and uniformly mixing; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the photochromic laser color change material. The temperature in the blending extrusion processing process is controlled between 170 ℃ and 240 ℃;
and then, directly carrying out injection molding on the obtained photochromic laser color change material granules in an injection molding machine, controlling the injection molding temperature to be 180-250 ℃ and preparing a black and gray standard sample plate.
Comparative example 10
Matrix polymer: polypropylene (PP), china petrochemical, lanzhou division, T30S;
carbon material: graphite with a mesh number of 2000;
core-shell structure microspheres (PCC-7): when stimulated by ultraviolet rays, the color of the material is changed from colorless to red. The polyformaldehyde resin is a shell of the microsphere, the photochromic compound is a diarylethene compound, the solvent is toluene, and the light stabilizer is a light stabilizer 622, and the three form a core of the microsphere. The particle size of the core-shell microsphere is 12 μm.
100 parts by weight of polypropylene resin, 6 parts by weight of core-shell structure microspheres and 15 parts by weight of graphite powder are placed in a high-speed mixer and uniformly mixed; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the photochromic laser color change material. The temperature in the blending extrusion processing process is controlled between 170 ℃ and 240 ℃;
and then, directly carrying out injection molding on the obtained photochromic laser color change material granules in an injection molding machine, controlling the injection molding temperature to be 180-250 ℃ and preparing a black standard sample plate.
Comparative example 11
Matrix polymer: polypropylene (PP), china petrochemical, lanzhou division, T30S;
carbon material: graphite with mesh number of 2000;
core-shell structure microspheres (PCC-1-1): when stimulated by ultraviolet rays, the color of the material is changed from colorless to blue. The melamine formaldehyde resin is the shell of the microsphere, the photochromic compound is a spiropyran compound, the solvent is ethyl decanoate, the light stabilizer is bisphenol A, and the three form the core of the microsphere. The particle size of the core-shell structure microsphere is 400 nm;
100 parts by weight of polypropylene resin, 6 parts by weight of core-shell structure microspheres and 0.2 part by weight of graphite are placed in a high-speed mixer and uniformly mixed; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the photochromic laser color change material. The temperature in the blending extrusion processing process is controlled between 170 ℃ and 240 ℃;
and then, directly carrying out injection molding on the obtained photochromic laser color change material granules in an injection molding machine, controlling the injection molding temperature to be 180-250 ℃ and preparing a black standard sample plate.
Comparative example 12
Matrix polymer: polypropylene (PP), china petrochemical, lanzhou division, T30S;
carbon material: graphite with a mesh number of 2000;
core-shell structure microspheres (PCC-1-3): when stimulated by ultraviolet rays, the color of the material is changed from colorless to blue. The melamine formaldehyde resin is the shell of the microsphere, the photochromic compound is a spiropyran compound, the solvent is ethyl decanoate, the light stabilizer is bisphenol A, and the three form the core of the microsphere. The particle size of the core-shell structure microsphere is 110 mu m;
100 parts by weight of polypropylene resin, 6 parts by weight of core-shell structure microspheres and 0.2 part by weight of graphite are placed in a high-speed mixer and uniformly mixed; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the photochromic laser color change material. The temperature in the blending extrusion processing process is controlled between 170 ℃ and 240 ℃;
and then, directly carrying out injection molding on the obtained photochromic laser color change material granules in an injection molding machine, controlling the injection molding temperature to be 180-250 ℃ and preparing a black standard sample plate.
Experimental example laser marking Effect test
1. Experimental methods
The standard samples prepared in all examples and comparative examples were evaluated for laser marking using the following conditions. The laser scanning speed is 1000mm/s, the laser energy is 10W, and the laser frequency is 100 kHz. The formulation composition and laser marking effect of all examples and comparative examples are shown in table 1. The marking effect refers to the color difference between the marked area and the dark base.
In the evaluation of the effect of the photochromic laser marking, the larger the number of "+" is, the better the effect of the laser marking is.
2. Results of the experiment
The formula of the photochromic laser color-changing material and the evaluation result of the photochromic laser mark are shown in table 1, wherein core-shell structure microspheres and carbon materials are given in percentage by weight, and the balance is matrix polymer. It can be seen that by selecting a reasonable ratio of the carbon material to the core-shell structure microspheres, the photochromic laser marking effect produced in the example is far superior to that of the sample prepared in the comparative examples 1 to 8. Especially, the color development effect of the laser mark of examples 5 to 8 was the best.
TABLE 1 evaluation results of laser marking effects
In summary, the invention discloses a novel photochromic laser color-changing material, which combines a matrix polymer, a carbon material and core-shell structure microspheres, and makes the material mark white or light-colored patterns or characters on a dark-colored polymer by using laser through specific proportion and material selection, and the patterns or characters can become colored patterns or characters under the stimulation of ultraviolet light and/or visible light. The photochromic laser color change material has the advantages of simple and efficient preparation process, simple and convenient operation, safety, environmental protection and low energy consumption, and is very suitable for industrial large-scale production.
Claims (10)
1. The photochromic laser color-changing material is characterized by being prepared from the following raw materials in parts by weight:
93.8 to 96.95 portions of matrix polymer,
0.05 to 0.2 portion of carbon material,
3-6 parts of core-shell structure microspheres;
the shell material of the core-shell structure microsphere is thermosetting resin, and the core of the core-shell structure microsphere is composed of a photochromic compound, a solvent and a light stabilizer;
the matrix polymer is selected from polyethylene, polypropylene, ethylene-propylene copolymer, polyformaldehyde, polystyrene, styrene-acrylonitrile copolymer, styrene-methyl methacrylate copolymer, polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate, polycarbonate, polyester elastomer, polybutylene succinate-butylene terephthalate, polybutylene succinate-butylene adipate, polymethacrylate-butadiene-styrene copolymer, styrene-acrylonitrile-acrylate copolymer, methacrylate-butadiene-styrene, polyethylene terephthalate-butadiene-styrene copolymer, polyethylene terephthalate-acrylonitrile-acrylate copolymer, polyethylene terephthalate-butadiene-styrene, polyethylene terephthalate, polyethylene, At least one of ABS, nylon, polyolefin elastomer, ethylene-vinyl alcohol copolymer, ethylene-vinyl acetate copolymer, SEBS, SEPS and SEEPS;
the carbon material is selected from at least one of graphite, graphene, carbon black and carbon nanotubes;
the thermosetting resin is at least one of urea-formaldehyde resin, phenolic resin, melamine-formaldehyde resin, chitosan, epoxy resin or unsaturated or polyester resin;
the photochromic compound is at least one selected from a spiropyran compound, a spirooxazine compound, a fulgide compound, a diarylethene compound, an azobenzene compound, a Schiff base compound, a bisanthrone compound, a fluorescent hydrocarbon compound, a triphenylmethane compound or a cholesteric liquid crystal compound;
the solvent is at least one selected from liquid paraffin, ethyl heptanoate, ethyl octanoate, ethyl nonanoate, ethyl decanoate, ethyl palmitate, methyl heptanoate, methyl octanoate, methyl nonanoate, methyl decanoate, methyl palmitate, dichloromethane, trichloromethane, cyclohexane, benzene, toluene, xylene or decalin;
the particle size of the core-shell structure microsphere is 500 nm-100 mu m.
2. The photochromic laser color-changing material of claim 1, which is prepared from the following raw materials in parts by weight:
93.8 to 96.8 portions of matrix polymer,
0.2 part of carbon material (C),
3-6 parts of core-shell structure microspheres.
3. The photochromic laser-color change material according to claim 1 or 2, wherein: the grain diameter of the core-shell structure microsphere is 800 nm-80 μm.
4. A method for preparing a photochromic laser-color change material according to any one of claims 1 to 3, comprising the steps of: and uniformly mixing the matrix polymer, the carbon material and the core-shell structure microspheres, and then melting, extruding and granulating to obtain the core-shell structure microsphere.
5. The method of claim 4, wherein: the melting and extrusion is carried out in an internal mixer or an extruder, and/or the extrusion conditions are at a temperature of 160 ℃ to 270 ℃.
6. Use of the photochromic laser color-changing material of any one of claims 1 to 3 in the manufacture of a security marking.
7. A preparation method of an anti-counterfeiting mark is characterized by comprising the following steps: it is made by irradiating the photochromic laser color-changing material according to any one of claims 1 to 3 with laser light and producing a pattern or text having a color lighter than the original surface.
8. The method of claim 7, wherein: the laser passes CO2Laser, Nd YAG laser, Nd YVO4 laser, excimer laser, fiber laser, diode array laser or diode laser; the wavelength of the laser is 157nm-10.6 μm.
9. The method of claim 8, wherein: the laser is emitted by a pulse Nd-YAG laser or a pulse fiber laser; the wavelength of the laser is 1064nm, 532nm or 355 nm.
10. The anti-counterfeiting mark obtained by the preparation method of any one of claims 7 to 9.
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| US6525136B1 (en) * | 2001-08-02 | 2003-02-25 | Xerox Corporation | Photochromic core and shell matrix |
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